KR20120000093A - Heat-shrinkable polyester tubing - Google Patents

Abstract

Providing a polyester-based heat shrinkable tube that is particularly excellent in practical heat resistance and satisfies characteristics required for heat shrinkable tubes such as electrical properties, chemical resistance and electrolyte resistance. The secret of the crystalline polyester (a) whose main component of the acid component is terephthalic acid and the main component of the diol component is ethylene glycol, and the copolymer component other than ethylene glycol as the main component of the acid component is terephthalic acid. Consisting of a resin composition (A) containing qualitative polyester (b) as a main component, the value of fusion enthalpy ΔHm in the re-heating process measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121 is 15 J / g or more. It is set to 35 J / g or less.

Description

Polyester Heat Shrinkable Tube {HEAT-SHRINKABLE POLYESTER TUBING}

The present invention relates to a polyester-based heat-shrinkable tube, and more particularly, to a polyester-based heat-shrinkable tube which is particularly excellent in practical heat resistance and suitable for coating capacitors such as electronic components, particularly aluminum electrolytic capacitors. .

Conventionally, the heat shrinkable tube which mainly consists of polyvinyl chloride resin has been used for the electrical insulation material for covering electronic components, such as a capacitor | condenser and a battery. However, in the recent trend of miniaturization and thinning, the mounting on electronic boards has become denser, and the use environment has become very strict than in the past due to self-heating, thermal stress from the surroundings, and the like. Heat resistance has been required. Polyvinyl chloride resin tubes are inexpensive but have insufficient heat resistance, and there is a concern about environmental problems caused by the generation of hydrogen chloride gas at the time of combustion, and as a replacement of polyvinyl chloride resin heat shrinkable tubes, polyethylene terephthalate resin thermal shrinkage Sex tubes have been intended to be used.

The characteristics required for the heat shrink tube used for the insulating material for electronic components such as a capacitor are required to have characteristics such as coating finish, heat resistance, chemical resistance, and electrolyte resistance. For example, Patent Literature 1 discloses a heat shrink tube that completely adheres to a groove of a capacitor even in dry heat treatment after coating and washing the capacitor, containing 9 to 15 mol% of neopentyl glycol as a diol component. A heat shrink tube made of polyethylene terephthalate has been proposed. Moreover, in patent document 2, in order to improve the heat resistance in a reflow furnace, the crystallization degree after heat-processing 105 degreeC x 30 minutes is 16% or less, and melting point peak temperature of aromatic polyester resin calculated | required by DSC measurement is 220 degreeC or more. A heat shrink tube characterized by the above is proposed.

However, in heat shrink tubes used for insulating materials for electronic components such as capacitors, the heat resistance at the time of capacitor manufacturing processes and substrate mounting has not yet been sufficient. For example, when an electrolytic solution or dirt is adhered to a condenser coated with a heat shrink tube, and the heat treatment is performed, or when mounting the substrate through a solder reflow furnace after flux-cleaning the solder adhesion surface when mounting the substrate. There was a problem that a part of the tube was expanded, wrinkled, or the like.

Japanese Patent Application Laid-Open No. 09-148177 Japanese Patent Publication No. 2002-264210

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and the problem of the present invention is particularly excellent in practical heat resistance, which satisfies the properties required for heat shrinkable tubes such as electrical properties, chemical resistance, electrolyte resistance, and the like. It is in providing a tube.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining about polyester-based resin, the inventors discovered the polyester-type heat shrinkable tube which was especially excellent in practical heat resistance, and came to complete this invention.

That is, the subject of this invention is crystalline polyester (a) whose main component of an acid component is terephthalic acid, and the main component of a diol component is ethylene glycol, and ethylene glycol in a diol component as a main component of an acid component is terephthalic acid. Melting enthalpy ΔHm in the re-heating process, which is composed of a resin composition (A) mainly composed of amorphous polyester (b) containing other copolymerization components, and measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121. Is achieved by a polyester-based heat-shrinkable tube (hereinafter also referred to as the "tube of the present invention") having a value of 15 J / g or more and 35 J / g or less.

As for the tube of this invention, it is preferable that content of amorphous polyester (b) is 1 mass% or more and 40 mass% or less with respect to 100 mass% of said resin compositions (A).

It is preferable that the tube of this invention contains crystalline polyester (c) whose main component of an acid component is terephthalic acid, and the main component of a diol component is 1, 4- butanediol.

As for the tube of this invention, it is preferable that amorphous polyester (b) contains the diol component which has alicyclic structure as a diol component.

In the tube of the present invention, the diol component having the alicyclic structure is preferably 1,4-cyclohexanedimethanol.

According to the present invention, it is possible to provide a polyester-based heat-shrinkable tube that is particularly excellent in practical heat resistance and satisfies characteristics required for heat-shrinkable tubes such as electrical properties, chemical resistance, and electrolyte resistance. Therefore, this invention is useful as a coating material of electronic components including capacitors, such as an aluminum electrolytic capacitor.

Hereinafter, the tube of this invention is demonstrated in detail.

In the tube of the present invention, the crystalline polyester (a) wherein the main component of the acid component is terephthalic acid and the main component of the diol component is ethylene glycol, and the main component of the acid component is terephthalic acid and other than ethylene glycol in the diol component. The value of the melting enthalpy ΔHm during the re-heating process, which is composed of a resin composition (A) mainly containing amorphous polyester (b) containing a copolymerization component, and measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121. It is characterized by being 15 J / g or more and 35 J / g or less.

1. Resin composition (A)

The resin composition (A) used in the tube of this invention is crystalline polyester (a) whose main component of an acid component is terephthalic acid, and the main component of a diol component is ethylene glycol, and the main component of an acid component is terephthalic acid, and a diol. A component contains amorphous polyester (b) which contains copolymerization components other than ethylene glycol as a main component.

<Crystalline polyester (a)>

In the present invention, the crystalline polyester is heated to a heating rate of 10 ° C./min from -50 ° C. to 300 ° C. using DSC according to JIS-K7121, and held at 300 ° C. for 1 minute, and then cooled to −50 ° C. The polyester-based resin which exhibits a clear melting peak at the second temperature rise when the temperature is lowered at a rate of 10 ° C./min, is maintained at −50 ° C. for 1 minute, and then heated up to 300 ° C. at a heating rate of 10 ° C./min. Point to. In the copolymerization component of the crystalline polyester (a), the acid component contains terephthalic acid as a main component, and the diol component contains ethylene glycol as a main component. Terephthalic acid and ethylene glycol which are main components are contained in the ratio of 51 mol% or more, Preferably 70 mol% or more, More preferably, 80 mol% or more in an acid component or a diol component, respectively. In addition, the crystalline polyester (a) may contain another copolymerization component in the range of 49 mol% or less, Preferably it is 30 mol% or less, More preferably, 20 mol% or less in an acid component or a diol component.

As an example of the other acid component which can be copolymerized, isophthalic acid, 2-chloro terephthalic acid, 2, 5- dichloro terephthalic acid, 2-methyl terephthalic acid, 4, 4- steel bend dicarboxylic acid, 4, 4- biphenyl dicarboxylic acid, orthophthalic acid , 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxy Aromatic dicarboxylic acid components derived from ethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, adipic acid, sebaic acid, azelaic acid, dodecanediic acid, 1,3-cyclohexane And aliphatic dicarboxylic acid components derived from dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Among them, aromatic dicarboxylic acid components including isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable.

Moreover, as an example of the other diol component which can be copolymerized, diethylene glycol, a 1, 2- propylene glycol, 1, 3- propanediol, 2, 2- dimethyl- 1, 3- propane Diol, trans-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neophene Tilglycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, 1, 4-cyclohexanediol, 1,3-cyclohexanediol, spiroglycol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2- And diol components derived from hydroxyethyl ether). Especially, diethylene glycol, 1, 3- propanediol, etc. are preferable.

These crystalline polyester (a) can also be used individually by 1 type or in mixture of 2 or more types.

Examples of commercially available products of the crystalline polyester (a) include "Novapex" series (manufactured by Mitsubishi Chemical Corporation), "unipet" (manufactured by Nippon Unipet Co., Ltd.), and the like.

 <Amorphous Polyester (b)>

In the present invention, amorphous polyester is heated to a heating rate of 10 deg. C / min from -50 deg. C to 300 deg. C using DSC according to JIS-K7121, and held at 300 deg. C for 1 minute, and then cooled to -50 deg. When the temperature was lowered at a rate of 10 ° C./min, held at −50 ° C. for 1 minute, and then raised to 300 ° C. at a heating rate of 10 ° C./min, the polyester system did not show a clear melting peak at the second temperature increase. Point to the resin. The acid component of the amorphous polyester (b) has terephthalic acid as a main component, the diol component has ethylene glycol as a main component, and 1 mol% or more, preferably 15 mol% or more of copolymerization components other than ethylene glycol, More preferably, it is 25 mol% or more, and contains 49 mol% or less, Preferably it is 45 mol% or less.

The other acid component and diol component which can be copolymerized are the same as the component shown by the said crystalline polyester (a), but the diol component is diethylene glycol and a trans- tetramethyl- 1, 3- cyclobutane Diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexane It is preferable that it is 1 or more types chosen from the group which consists of dimethanol, 1, 4- cyclohexanediol, 1, 3- cyclohexanediol, a spiro glycol, and polytetramethylene glycol. In particular, trans-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, 1, Suitable diol components having at least one alicyclic structure selected from the group consisting of 3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol and spiroglycol 1,4-cyclohexanedimethanol and spiroglycol are particularly preferred from the viewpoint of economical efficiency, industrial availability, and mixing with crystalline polyester (a).

Here, the content rate of the diol component which has alicyclic structure is 1 mol% or more, Preferably it is 15 mol% or more, More preferably, it is 25 mol% or more in all the diol components of an amorphous polyester (b), and an upper limit is 49 mol%. Hereinafter, it is preferable that it is the range of 45 mol% or less preferably. If the content rate of the diol component which has an alicyclic structure is the said range, after heating up from -50 degreeC to 300 degreeC at a heating rate of 10 degree-C / min using DSC, and holding at 300 degreeC for 1 minute according to JIS-K7121, When the temperature was lowered to -50 ° C at a cooling rate of 10 ° C / min, held at -50 ° C for 1 minute, and then raised to 300 ° C at a heating rate of 10 ° C / min, a clear melting peak appeared at the second temperature increase. It can be set as resin which does not appear.

Moreover, in the tube of this invention, it is preferable that the glass transition temperature (Tg) of amorphous polyester (b) is 80 degreeC or more and 120 degrees C or less, and it is more preferable that Tg is higher than crystalline polyester (a) to be used. . If the glass transition temperature (Tg) of the amorphous polyester (b) is within the above range, the enthalpy ΔHm value of the melting composition of the resin composition (A) is determined by the heat resistance and the content of the amorphous polyester (b) derived from the high Tg. Since it is easy to control, since it can satisfy the (1) flux swelling test, (2) washing swelling test, and (3) high temperature standing test mentioned later at the same time, it is preferable.

As a commercial item of an amorphous polyester (b), for example, "Eastar Copolyester 6763", "Eastar Copolyester GN001" (made by Eastman Chemical Co., Ltd.), "TRITAN" (made by Eastman Chemical Co., Ltd.), "SKYGREEN PETG S2008" (SK Chemical Co., Ltd.) Products), "ALTESTER" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

Content of the amorphous polyester (b) contained in a resin composition (A) is 1 mass% or more with respect to 100 mass% of total of a crystalline polyester (a) and an amorphous polyester (b), Preferably it is 5 It is mass% or more, More preferably, it is 10 mass% or more, 40 mass% or less, Preferably it is 35 mass% or less, More preferably, it can be 30 mass% or less. If content of amorphous polyester (b) is in the said range, the heat resistance excellent in practical use can be provided to resin composition (A), without impairing the characteristic of crystalline polyester, such as chemical resistance.

<Crystalline polyester (c)>

The tube of the present invention may further include a crystalline polyester (c) in which the main component of the acid component is terephthalic acid and the main component of the diol component is 1,4-butanediol in the resin composition (A). By containing the crystalline polyester (c) in the resin composition (A), the glass transition temperature Tg and the crystallization rate of the resin composition (A) can be adjusted. In order to acquire such an effect, it is preferable to make content rate of a crystalline polyester (c) into 20 mass% or less with respect to 100 mass% of resin compositions (A), Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less. desirable.

As a commercial item of the crystalline polyester (c), "Nova Duran" (made by Mitsubishi Chemical Engineering Plastics Co., Ltd.), "Juranex" (made by Wintech Polymers), etc. are mentioned, for example.

Moreover, the tube of this invention contains resin other than resin composition (A) (for example, resins including thermoplastic elastomers, such as polyester type, an olefin copolymer, and polystyrene type), unless the effect of this invention is impaired. You may. In addition, another component can also be added to a resin composition (A) suitably according to a use. For example, organic lubricants, inorganic lubricants, inorganic fillers, or impact resistance enhancers, fillers, ultraviolet absorbers, surface treatment agents, light stabilizers, pigments, antistatic agents, and antibacterial agents for improving the activity in the tube. Preparations such as a crosslinking agent, an antioxidant, a flame retardant, a plasticizer, a processing aid, and a blowing agent can be blended.

2. Fusion Enthalpy ΔHm

According to JIS-K7121, the tube of the present invention has a value of fusion enthalpy ΔHm of 15 J / g or more, preferably 18 J / g or more, more preferably 20 J / g or more in the re-heating process measured by DSC, 35 J / g or less. The tube of this invention can express heat resistance when the value of fusion enthalpy (DELTA) Hm exists in the said range, and it can use suitably as a coating material of a capacitor | condenser and a battery by this. When the enthalpy ΔHm value exceeds 35 J / g, when exposed to high temperatures such as capacitors or the like, the tube once in close contact with the capacitor or the like will loosen due to crystal growth. do. Moreover, when it is less than 15 J / g, the characteristic of crystalline resin, such as heat resistance and chemical resistance, may be impaired.

As means for bringing the value of the fusion enthalpy ΔHm of the tube of the present invention into the above range, the copolymerization composition of the crystalline polyester (a) in the resin composition (A), the combination of the amorphous polyester (b) and other resins, The method of adjusting a compounding ratio and intrinsic viscosity is mentioned. In this invention, the method of adjusting the copolymerization composition of the crystalline polyester (a) in a resin composition (A), or the method of adjusting the compounding ratio of a resin composition (A) is used suitably. For example, when it is desired to increase the melting enthalpy ΔHm, the content of the crystalline polyester (a) is increased, the content of the amorphous polyester (b) is reduced, and if necessary, the crystalline polyester (c) is reduced. Means to reduce the kind of monomer used for an acid component and a diol component in the technique to contain and the copolymerization composition of the crystalline polyester (a) in a resin composition (A) are mentioned. In addition, when it is desired to reduce the melting enthalpy ΔHm, a method of reducing the content of the crystalline polyester (a) and increasing the content of the amorphous polyester (b) or the crystalline polyester in the resin composition (A) ( Means, such as increasing the kind of monomer used for an acid component and a diol component in the copolymerization composition of a), are mentioned. For example, in the case of homo PET (100 mol% terephthalic acid and 100 mol% ethylene glycol), which is a crystalline polyester (a), the value of the fusion enthalpy ΔHm is usually in the range of 45 J / g or more and 60 J / g or less. The value of ΔHm can be reduced by adjusting the type and number of monomers used in the acid component and the diol component of the copolymerization composition.

However, when ΔHm is to be controlled only by the method of adjusting the copolymerization composition of the crystalline polyester (a) to be used, the melting temperature Tm is also lowered and the heat resistance as the whole resin composition (A) is lowered. Thus, the amorphous polyester (b) is used. It is more preferable to use together and adjust content.

In addition, the kind and content of the acid component and diol component which are copolymerization components can be qualitatively quantitatively analyzed by a well-known method, for example, a nuclear magnetic resonance (NMR) measuring apparatus, and other apparatus analyzers.

The fusion enthalpy ΔHm was raised from -50 ° C to 300 ° C at a heating rate of 10 ° C / min at a heating rate of 10 ° C / min in accordance with JIS-K7121, using a Perkin Elmer company DSC-7. After holding at 1 ° C for 1 minute, the temperature was lowered to -50 ° C at a cooling rate of 10 ° C / min, maintained at -50 ° C for 1 minute, and then thermally analyzed when heated up to 300 ° C at a heating rate of 10 ° C / min. Available from

3. Manufacturing method of the tube of the present invention

The manufacturing method of the tube of this invention can be formed into a film by a normal tube manufacturing method, and it is achieved by melt-molding the polyester raw material mentioned above, and extruding it by cylindrical shape from an annular die to tubular shape, and forming. The tube of the present invention, the unstretched tube in the radial direction of 1.2 times or more, preferably 1.3 times or more, more preferably 1.4 times or more, 3.0 times or less, preferably 2.5 times or less, more preferably 2.0 times It is preferable that it is obtained by extending | stretching in the range of the following range and the length direction 1.0 times or more, Preferably it is 1.02 times or more, 2.0 times or less, Preferably it is 1.5 times or less, More preferably, 1.3 times or less. . Here, when the draw ratio in the radial direction of the tube is 1.2 times or more, the amount of shrinkage sufficient for coating is obtained, and when it is 3.0 times or less, the tendency to increase the thickness variation can be suppressed, and the shrinkage rate due to the orientation crystallization is lowered. Can be suppressed. On the other hand, if the draw ratio in the longitudinal direction of the tube is 2.0 times or less, the shrinkage amount in the longitudinal direction increases, and thus the cost increase is suppressed because there is no need to lengthen the phenomenon or the length of cut when the coating position is shifted when coating the electronic component or the like. can do.

Although the thickness of the tube obtained as mentioned above is not specifically limited, Generally, the thickness of the tube used for a capacitor | condenser is a range of about 0.05 mm-1.0 mm, typically 0.07 mm-0.2 mm depending on the rated voltage of a capacitor | condenser. The thing of the range of is used. Moreover, it is preferable that the width | variety (henceforth "folding diameter") of the state which folded a tube of the range of 4 mm-300 mm can respond to general purpose capacitor | condenser, battery coating, and general packaging of general purpose battery.

4. Characteristics of the Tube of the Invention

The tube of the present invention is composed of the above resin composition and has a specific heat shrinkage, which is particularly excellent as a covering material of a capacitor or a battery.

(1) The shrinkage in the longitudinal direction when immersed in hot water at 100 ° C. for 10 seconds is 2% or more, preferably 3% or more, more preferably 5% or more, 20% or less, preferably 15% or less, More preferably, it is 12% or less of range. The shrinkage in the radial direction is 15% or more, preferably 20% or more, more preferably 25% or more, 60% or less, preferably 50% or less, more preferably 45% or less.

More preferably, it satisfies the following characteristics as in (1).

(2) The shrinkage in the longitudinal direction when immersed in warm water at 80 ° C. for 10 seconds is 2% or more, preferably 3% or more, more preferably 5% or more, 15% or less, preferably 12% or less, More preferably, it is 10% or less of range. The shrinkage in the radial direction is 10% or more, preferably 15% or more, more preferably 20% or more, 60% or less, preferably 50% or less, and more preferably 45% or less.

Tubes which do not satisfy the heat shrinkage characteristics of (1) above, preferably the heat shrinkage characteristics of (1) and (2), have poor coating appearance and require a large amount of heat when they are coated on a coating object, thereby reducing energy costs. This tends to be high. If the characteristics of (1) and (2) are satisfied, it becomes possible to coat | cover on substantially the same conditions as a PVC tube using the existing coater.

In addition, since the tube of the present invention has a fusion enthalpy ΔHm value in a predetermined range, no expansion of the heat shrinkable tube after the end of the capacitor manufacturing process or the end of the process at the time of mounting the substrate occurs, and it has heat resistance in practical use, and thus has a capacitor or a battery. Is excellent as a coating material.

(1) Here, the cleaning swelling test is a test method for evaluating the expansion of the heat shrinkable tube in the capacitor manufacturing process. Specifically, after covering 3.6 seconds with a 300 degreeC nichrome wire heater, it was immersed continuously in normal temperature water for 15 minutes, 60 degree hot water for 30 minutes, and further 15 minutes in normal temperature water for 60 minutes in a 95 degreeC atmosphere in a hot air circulation type oven. After exposure, the appearance of the coated heat shrinkable tube (hereinafter also referred to as "coated tube") is visually evaluated. The cause of the expansion of the heat-shrinkable tube after the cleaning swelling test was that water was infiltrated into the gap between the coated tube and the condenser when immersed in two room temperature water and 60 ° C hot water, and then exposed to a 95 ° C atmosphere in a hot air circulation oven. At this time, since the water which penetrated the gap evaporates and the volume increases, it is estimated that the pressure of the gap between the covering tube and the condenser increases, causing expansion of the covering tube.

(2) The flux swell test is a test method for evaluating the expansion of a tube during substrate mounting. Specifically, the coating was coated with a 300 ° C. nichrome wire heater for 3.6 seconds, and heat-treated in a hot air circulation oven for 60 minutes in an 85 ° C. atmosphere, and then the flux (for example, Koki JS-E Co., Ltd.) on the sealing part of the condenser. -11) was applied to the substrate so that the substrate and the condenser sealing portion were in close contact with each other, and the appearance of the coated tube after exposure for 2 minutes in a hot air circulation oven under a 160 ° C atmosphere was visually evaluated. The cause of expansion of the tube after the flux swelling test is that when the flux applied to the sealing portion of the condenser penetrates into the gap between the covering tube and the condenser and is exposed to a 160 ° C. atmosphere in a subsequent hot air circulation oven, the covering tube and the condenser Since the flux which penetrated in between evaporates and the volume increases, it is estimated that the pressure of the gap between the covering tube and the condenser increases, causing expansion of the covering tube.

(3) The high temperature standing test is a test method for evaluating heat resistance, which is coated with a 300 ° C. nichrome wire heater for 3.6 seconds and subjected to aging for 60 minutes in an 85 ° C. atmosphere using a hot air circulation oven, followed by a hot air circulation oven. The external appearance of the coating tube after exposing for 60 minutes in 150 degreeC atmosphere is evaluated visually. The cause of expansion of the tube after the high-temperature standing test is that in a conventional polyethylene terephthalate resin heat-shrinkable tube, crystallization proceeds when exposed to a 150 ° C. atmosphere in a hot air circulation oven, and the expansion between the crystal itself and the interference between the crystals Since much of this occurs, it is assumed that the volume of the tube increases, causing expansion of the coated tube.

The heat shrinkable tube that does not pass any of the above (1) flux swelling test, (2) cleaning swelling test, and (3) high temperature standing test may cause expansion of the tube after the end of the capacitor manufacturing process or the process at the time of mounting the substrate. Therefore, it cannot be mounted and the heat resistance in real use worsens. On the contrary, if it is a heat shrinkable tube which passes all the tests of said (1), (2), and (3), it can mount process without damaging the external appearance of the coating tube after the process of capacitor | condenser manufacture or completion | finish of board | substrate mounting.

In order to pass all the tests of (1), (2) and (3) above, in the tube of the present invention, the copolymer composition of the crystalline polyester (a), the combination of the amorphous polyester (b) and other resins, The blending ratio is adjusted, and the value of the fusion enthalpy ΔHm in the reheating process measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121 is 15 J / g or more and 35 J / g or less, preferably 20 J / g or more and 35 J / It is set to g or less.

5. Tube coated member of the present invention

Although the tube of this invention can be used suitably for coating | covering capacitor | condensers, such as an aluminum electrolytic capacitor, other uses, such as a secondary battery, steel pipes, such as an electric wire (ring line, a square wire), a dry cell, a lithium ion battery, or It can also be used as an electric device such as a motor coil end, a transformer, a small motor, or a tube for fluorescent lamp coating of a light bulb, a fluorescent lamp, a facsimile or an image scanner.

In addition, when it expresses as a "main component" in this invention, it contains the intention that it may contain components other than a main component. Although the content ratio with respect to all components is not specifically limited, It is necessary to occupy at least 50% (mol% or mass%) of all components (when the main component is two components or more, the sum totals 50% or more), especially 60% The above is preferable, and it is especially preferable to occupy 70% or more, especially 90% or more (including 100%) among these.

Example

Although an Example demonstrates further in detail below, this invention is not restrict | limited at all by these.

In addition, the various measurement values and evaluation about the heat shrinkable tube shown in this specification were performed as follows.

(1) Glass transition temperature Tg and melting enthalpy ΔHm

Melting enthalpy ΔHm is 300 mg from -50 ° C at a heating rate of 10 ° C / min, according to JIS-K7121, for 10 mg of sample cut out from the film-formed heat-shrinkable tube using Perkin Elmer Corporation DSC-7 according to JIS-K7121. The temperature was raised to 0 ° C., held at 300 ° C. for 1 minute, the temperature was lowered to −50 ° C. at a cooling rate of 10 ° C./min, and maintained at −50 ° C. for 1 minute, and then again raised to 300 ° C. at a heating rate of 10 ° C./min. It calculated | required from the thermal analysis diagram at the time of letting.

Also about glass transition temperature Tg, it calculated | required similarly to (DELTA) Hm according to JIS-K7121.

(2) shrinkage

The length and folding diameter of the heat-shrinkable tube before and after immersing in warm water at 100 ° C or 80 ° C for 10 seconds were measured and calculated.

Longitudinal shrinkage [%] = [(length of tube before immersion-length of tube after immersion) / length of tube before immersion] × 100

Radial shrinkage [%] = [(folding diameter of pre-immersion tube-folding diameter of tube after immersion) / folding diameter of tube before immersion] × 100

(3) flux swelling test

An aluminum electrolytic capacitor having a diameter of 5 mm and a length of 11.0 mm was coated with a folded diameter of 8.6 mm, a thickness of 0.07 mm, and a length of 14.7 mm for 3.6 seconds with a nichrome wire heater at 300 ° C, and heat treated for 60 minutes in an 85 ° C atmosphere using a hot air circulation oven. Done. Thereafter, flux (Koki JS-E-11) was applied to the sealing portion of the condenser, and the substrate and the condenser sealing portion were attached to the substrate so as to be in close contact with each other under a 160 ° C atmosphere in a hot air circulation oven for 2 minutes. The external appearance of the condenser covering tube after heating was visually evaluated as follows.

(○) The tube has no swelling or loosening, and the appearance of the coating is good.

(X) Swelling, loosening, etc. occur remarkably in the tube and cannot be used because of poor appearance.

(4) cleaning swelling test

An aluminum electrolytic capacitor having a diameter of 10 mm and a length of 12.5 mm was coated with a folded diameter of 16.8 mm, a thickness of 0.08 mm, and a length of 16.1 mm for 3.6 seconds with a 300 ° C. nichrome wire heater, followed by water at room temperature for 15 minutes and hot water at 60 ° C. It was immersed continuously for 30 minutes in water of normal temperature further 15 minutes. Then, it exposed for 60 minutes in 95 degreeC atmosphere in hot-air circulation type oven, and visually evaluated the external appearance of the condenser coating tube after heating as follows.

(○) Good appearance of the coating without swelling or loosening in the tube.

(X) Swelling, loosening, etc. occur remarkably in the tube and cannot be used because of poor appearance.

(5) high temperature leaving test

An aluminum electrolytic capacitor having a diameter of 10 mm and a length of 12.5 mm was coated with a folded diameter of 16.8 mm, a thickness of 0.08 mm, and a length of 16.1 mm for 3.6 seconds with a 300 ° C. nichrome wire heater, and a 60 minute atmosphere under an 85 ° C. atmosphere using a hot air circulation oven. After passing through aging, the resultant was further exposed to 60 minutes in a hot air circulation oven under a 150 ° C atmosphere, and the heat resistance was visually evaluated as follows.

(○) Good appearance of the coating without swelling or loosening in the tube.

(X) Swelling, loosening, etc. occur remarkably in the tube and cannot be used because of poor appearance.

(6) solvent resistance test

An aluminum electrolytic capacitor having a diameter of 10 mm and a length of 12.5 mm was coated with a folded diameter of 16.8 mm, a thickness of 0.08 mm, and a length of 16.1 mm for 3.6 seconds with a nichrome wire heater at 300 ° C, and heat treated for 60 minutes in an 85 ° C atmosphere using a hot air circulation oven. Done. After immersion in each test solvent for a predetermined time, the appearance of the condenser coated tube dried at room temperature for 1 hour was visually evaluated as follows.

Test Solvent 1: Acetone Soak Time: 30 seconds

Test solvent 2: Xylene immersion time: 5 minutes

(○) Good appearance without swelling or cracking in the tube.

Swelling, cracks, etc. occur remarkably in the (×) tube and cannot be used because of poor appearance.

[Resin Used in Examples and Comparative Examples]

PET 1: Novapex BK2180 (crystalline polyester, manufactured by Mitsubishi Chemical Corporation; acid component: 98.6 mol% of terephthalic acid, 1.4 mol% of isophthalic acid, diol component: ethylene glycol 97.3 mol%, diethylene glycol 2.7 mol %, Tg = 77.1 ° C, Tm = 250.8 ° C, [η] = 0.79 polyethylene terephthalate / isophthalate resin)

PET 2: Novapex GS900 (crystalline polyester, manufactured by Mitsubishi Chemical Corporation; acid component: 100 mol% of terephthalic acid, diol component: 98.1 mol% of ethylene glycol, 1.9 mol% of diethylene glycol, Tg = 82.1 ° C Polyethylene terephthalate resin with Tm = 255.3 ° C., [η] = 0.994)

PET 3: ALTESTER45 (amorphous polyester, manufactured by Mitsubishi Gas Chemical Co., Ltd .; acid component: terephthalic acid 100 mol%, diol component: ethylene glycol 49.7 mol%, diethylene glycol 6.3 mol%, spiroglycol 44.0 mol%, Tg = 101.8 占 폚, Tm = 107.3 占 폚, [η] = 0.732 amorphous polyethylene terephthalate resin)

PET 4: Eastar Copolyester GN001 (amorphous polyester, produced by Eastman Chemical Co., Ltd .; acid component: terephthalic acid 100 mol%, diol component: ethylene glycol 65.3 mol%, diethylene glycol 2.5 mol%, 1,4 32.2 mol% cyclohexanedimethanol, Tg = 72.7 ° C., [η] = 0.824 amorphous polyethylene terephthalate resin)

PET 5: Unipet IG154K (crystalline polyester, manufactured by Nippon Unipet Co., Ltd .; acid component: 94.7 mol% of terephthalic acid, 5.3 mol% of isophthalic acid, diol component: ethylene glycol 95.2 mol%, diethylene glycol 4.8 mol%, polyethylene terephthalate / isophthalate resin of Tg = 72.8 ° C, Tm = 232.0 ° C, [η] = 0.72)

PBT: Nova Duran 5550 (crystalline polyester, manufactured by Mitsubishi Chemical Engineering Plastics Co., Ltd .; acid component: 100.0 mol% of terephthalic acid, diol component: 92.0 mass% of 1,4-butanediol, polytetramethylene glycol 8.0 Polytetramethylene glycol copolymerized polybutylene terephthalate resin having a mass%, Tg = 57.0 ° C, Tm = 219.0 ° C, and [η] = 0.897.

Inorganic lubricant 1: Silica having an average particle diameter of 4.0 μm

Hydrolysis inhibitor 1: Starbakzol 100 (Rheinchem Co., Ltd .; high molecular weight polycarbodiimide compound)

[Examples 1 to 5 and Comparative Examples 1 to 4]

The resin composition adjusted by the mixing | blending shown in Table 1 is melt | dissolved in the extruder set to the cylinder temperature of 280 degreeC, extruded through a ring die, immersed in water, and it solidified by cooling, and obtains the original tube before extending | stretching. The one tube was subsequently heated with hot water at 90 ° C., stretched from 1.05 to 1.1 times in the longitudinal direction and 1.7 to 1.8 times in the radial direction, and then cooled to fold in diameter of 8.6 mm, thickness of 70 μm, or folding diameter of 16.8 mm, A polyester heat shrinkable tube having a thickness of 80 μm was obtained. Table 1 shows the results of evaluating the characteristics of the tube obtained by tube forming.

[Table 1]

From Table 1, the tubes of the present invention (Examples 1 to 5) had a good appearance without coating and swelling in the tube even at a high temperature, and also had a good swelling flux and a swelling test. Also in the tube, the appearance was good without swelling, cracking, or the like. On the other hand, the tube (Comparative Examples 1-4) whose value of melting enthalpy (DELTA) Hm in the reheating process measured by a differential thermal scanning calorimeter (DSC) outside the specification range of this invention is a flux swelling test, a cleaning swelling test, and a high temperature. It can be seen that any one or more of the characteristics of the neglect test and the solvent resistance test are inferior. From this, it turns out that the tube of this invention is a polyester type heat shrinkable tube which is especially excellent in practical heat resistance, and satisfy | fills the characteristic calculated | required by the heat shrinkable tube, such as electrical property, chemical resistance, and electrolyte resistance.

Claims (8)

The secret of the crystalline polyester (a) whose main component of the acid component is terephthalic acid and the main component of the diol component is ethylene glycol, and the copolymer component other than ethylene glycol as the main component of the acid component is terephthalic acid. Consisting of a resin composition (A) containing qualitative polyester (b) as a main component, the value of fusion enthalpy ΔHm in the re-heating process measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121 is 15 J / g or more. Polyester-based heat-shrinkable tube, characterized in that less than 35J / g. The method of claim 1,
The polyester type heat-shrinkable tube whose content of amorphous polyester (b) is 1 mass% or more and 40 mass% or less with respect to 100 mass% of said resin compositions (A). The method according to claim 1 or 2,
The polyester type heat-shrinkable tube in which the resin composition (A) further contains crystalline polyester (c) whose main component of an acid component is terephthalic acid and the main component of a diol component is 1, 4- butanediol. The method according to any one of claims 1 to 3,
Polyester-based heat-shrinkable tube in which amorphous polyester (b) contains the diol component which has alicyclic structure as a diol component. The method of claim 4, wherein
Polyester-based heat-shrinkable tube, wherein the diol component having an alicyclic structure is 1,4-cyclohexanedimethanol. The method of claim 4, wherein
A polyester-based heat-shrinkable tube wherein the diol component having the alicyclic structure is spiroglycol. A member coated with the polyester-based heat-shrinkable tube according to any one of claims 1 to 6. The method of claim 7, wherein
Members used for electronic or electrical equipment.